Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry

Colizza, Kevin; Mahoney, Keira E.; Yevdokimov, Alexander; Smith, James L.; Oxley, Jimmie C.

doi:10.1007/s13361-016-1466-1

Cited by 22 publications

(14 citation statements)

References 27 publications

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“…In addition, as recently reported by J. Oxley (), an acetonitrile may suppress ionization in positive ionization mode by suppressing formation of the protonated ions. Methanol was used for TATP analysis.…”

Section: Resultssupporting

confidence: 54%

Rapid Quantitative Analysis of Multiple Explosive Compound Classes on a Single Instrument via Flow‐Injection Analysis Tandem Mass Spectrometry

Ostrinskaya

Kunz

Clark

et al. 2018

Journal of Forensic Sciences

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A flow-injection analysis tandem mass spectrometry (FIA MSMS) method was developed for rapid quantitative analysis of 10 different inorganic and organic explosives. Performance is optimized by tailoring the ionization method (APCI/ESI), de-clustering potentials, and collision energies for each specific analyte. In doing so, a single instrument can be used to detect urea nitrate, potassium chlorate, 2,4,6-trinitrotoluene, 2,4,6-trinitrophenylmethylnitramine, triacetone triperoxide, hexamethylene triperoxide diamine, pentaerythritol tetranitrate, 1,3,5-trinitroperhydro-1,3,5-triazine, nitroglycerin, and octohy-dro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine with sensitivities all in the picogram per milliliter range. In conclusion, FIA APCI/ESI MSMS is a fast (<1 min/sample), sensitive (~pg/mL LOQ), and precise (intraday RSD < 10%) method for trace explosive detection that can play an important role in criminal and attributional forensics, counterterrorism, and environmental protection areas, and has the potential to augment or replace several of the existing explosive detection methods.

show abstract

Section: Resultssupporting

confidence: 54%

Rapid Quantitative Analysis of Multiple Explosive Compound Classes on a Single Instrument via Flow‐Injection Analysis Tandem Mass Spectrometry

Ostrinskaya

Kunz

Clark

et al. 2018

Journal of Forensic Sciences

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“…We postulate that this competitive mechanism hypothesis can explain the problem with the signal suppression in acetonitrile reported by other researchers. 11 − 13 We note here that different APCI geometries will influence the extent of this behavior. APCI sources that yield CH 3 CNH + instead of (CH 3 CN) 3 H + as the main product ion of acetonitrile will not yield such a strong decrease in the protonation pathway due to the lower PA of CH 3 CN (∼780 kJ mol –1 ) compared to (CH 3 CN) 3 .…”

Section: Resultsmentioning

confidence: 86%

Significance of Competitive Reactions in an Atmospheric Pressure Chemical Ionization Ion Source: Effect of Solvent

Valadbeigi

Causon

2022

J. Am. Soc. Mass Spectrom.

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Ionization of organic compounds with different structural and energetic properties including benzene derivatives, polycyclic aromatic hydrocarbons (PAHs), ketones, and polyenes was studied using a commercial atmospheric pressure corona discharge (APCI) ion source on a drift tube ion mobility-quadrupole-time-of-flight mass spectrometer (IM-QTOFMS). It was found that the studied cohort of compounds can be experimentally ionized via protonation, charge transfer, and hydride abstraction leading to formation of [M + H] + , [M] +• , and [M – H] + species, respectively. By experimentally monitoring the product ions and comparing the thermodynamic data for different ionization paths, it was proposed that NO + is one of the main reactant ions (RIs) in the ion source used. Of particular focus in this work were theoretical and experimental studies of the effect of solvents frequently used for analytical applications with this ion source (acetonitrile, methanol, and chloroform) on the ionization mechanisms. In methanol, the studied compounds were observed to be ionized mainly via proton transfer while acetonitrile suppressed the protonation of compounds and enhanced their ionization via charge transfer and hydride abstraction. Use of chloroform as a solvent led to formation of CHCl 2 + as an alternative reactant ion (RI) to ionize the analytes via electrophilic substitution. Density functional theory (DFT) was used to study the different paths of ionization. The theoretical and experimental results showed that by using only the absolute thermodynamic data, the real ionization path cannot be determined and the energies of all competing processes such as charge transfer, protonation, and hydride abstraction need to be compared.

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“…According to our results, compared with methanol, ACN would reduce the sensitivity of 25(OH)D by 50%. Although the mechanism has not been clarified, we supposed it may be concerned with the formation of ACN complexes (26). All things considered, methanol was applied as mobile phases.…”

Section: Methods Development and Methods Comparisonmentioning

confidence: 99%

New LC-MS/MS method with single-step pretreatment analyzes fat-soluble vitamins in plasma and amniotic fluid

Le¹,

Yuan²,

Zhang

et al. 2018

Journal of Lipid Research

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Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry

Cited by 22 publications

References 27 publications

Rapid Quantitative Analysis of Multiple Explosive Compound Classes on a Single Instrument via Flow‐Injection Analysis Tandem Mass Spectrometry

Rapid Quantitative Analysis of Multiple Explosive Compound Classes on a Single Instrument via Flow‐Injection Analysis Tandem Mass Spectrometry

Significance of Competitive Reactions in an Atmospheric Pressure Chemical Ionization Ion Source: Effect of Solvent

New LC-MS/MS method with single-step pretreatment analyzes fat-soluble vitamins in plasma and amniotic fluid

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